Pivaloyl chloride → HCID 13075116, compound

HRID 51170Notes

Reaction equation

HRID 51170 reaction equation
[C:1](Cl)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].Br[CH:9]([CH3:15])[C:10]([O:12][CH2:13][CH3:14])=[O:11]>C(OCC)C>[C:1]([CH:9]([CH3:15])[C:10]([O:12][CH2:13][CH3:14])=[O:11])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3]

Participants

4

Reactant 2

HCID 62493Pivaloyl chlorideHCID 79040Ethyl 2-bromopropionate

Product 1

HCID 13075116HCID 13075116, compoundYield 56.4%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A 500 mL 3-neck round-bottom flask was equipped with a reflux condensor and thermometer and purged with nitrogen. To it was charged 100 mL dry, deoxygenated diethyl ether and 4.4 g of zinc strips. This mixture was agitated in a water-filled sonicating bath for 5 minutes. To this was slowly added a mixture of 12.06 g pivaloyl chloride (0.10 mole), 18.1 g of ethyl 2-bromopropionate (0.10 mole, synthesized by the method of Strunk, R. J.; DiGiacomo, P. M.; Aso, K.; Kuivila, H. G. J Am. Chem. Soc., 1970, 92, 2849-2856.) and 100 mL of ethyl ether. The resulting mixture was refluxed 6 hours and stirred at room temperature overnight. The mixture was then successively extracted with cold 20% aqueous sulfuric acid, water and brine before drying over sodium sulfate. The solution was stripped to obtain 12.8 g of crude oil. This was distilled under vacuum to yield 10.5 g of ethyl 2-pivaloylpropionate. 1H NMR (CDCl3): δ4.103 (q, J=7.1 Hz, 2H), 3.959 (q, J=6.9, 1 Hz), 1.287 (d, J=7.0 Hz, 3H), 1.196 (t, J=7.1 Hz, 3H), 1.157 (s, 9H).

Workup

  1. customA 500 mL 3-neck round-bottom flask was equipped with a reflux condensor and thermometer
  2. custompurged with nitrogen
  3. additionTo it was charged 100 mL
  4. customdry
  5. customdeoxygenated diethyl ether and 4.4 g of zinc strips
  6. additionfilled
  7. customsonicating bath for 5 minutes
  8. additionTo this was slowly added
  9. customsynthesized by the method of Strunk, R
  10. temperatureThe resulting mixture was refluxed 6 hours
  11. stirringstirred at room temperature overnight
  12. extractionThe mixture was then successively extracted with cold 20% aqueous sulfuric acid, water and brine
  13. dry with materialbefore drying over sodium sulfate
  14. customto obtain 12.8 g of crude oil
  15. distillationThis was distilled under vacuum

Sources & evidence

ORD record
ord-eb443a21b9e141cd83057af33b38f6aa
Source dataset
uspto-grants-2004_03
Patent number
US06713573B2

Reaction notes

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